# US 2013/0158207 A1 · Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides

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- Number: US 2013/0158207 A1
- Document ID: US20130158207A1
- Status: Published application
- Kind: A1
- Application number: 13/765,550
- Filed: 2013-02-12
- Published: 2013-06-20
- Earliest claimed: 2008-10-22
- Assignees: Chevron Oronite Company LLC
- Inventors: Casey D. Stokes
- Web page: https://patentgrep.com/patent/US20130158207A1

## CPC

- C08F 8/32: by reaction with amines
- C08F 8/00: Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C)
- C08F 8/26: Removing halogen atoms or halogen-containing groups from the molecule
- C08F 8/34: Introducing sulfur atoms or sulfur-containing groups
- C08F 8/36: Sulfonation; Sulfation
- C08F 8/42: Introducing metal atoms or metal-containing groups
- C08F 110/10: Isobutene
- C08F 2810/30: leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
- C08F 2810/40: taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Provided herein are methods for preparing vinylidene-terminated polyolefins. Further provided herein are sulfide-terminated polyolefins.

## Claims

### Claim 1

A method for preparing a compound of formula V:
wherein:
R1 is a polyolefin group; and
RC2 is alkyl, aryl, aralkyl, alkaryl, substituted alkyl, or substituted aryl;
comprising:
(a) ionizing a polyolefin in the presence of a Lewis acid or mixture of Lewis acids to form an ionized polyolefin;
(b) reacting the ionized polyolefin with one or more compounds of formula VI:
RA—S—S—RB VI
to form an intermediate;
wherein RA and RB are each, independently, alkyl, aryl, aralkyl, or alkaryl; and
(c) reacting the intermediate from step (b) with one or more compounds of formula VII.
RC2—SH VII

### Claim 2 (depends on 1)

The method of claim 1, wherein R1 is a polyisobutylene group.

### Claim 3 (depends on 1)

The method of claim 1, wherein RC2 is alkyl and RA and RB are each, independently, alkyl, aryl, or alkaryl.

### Claim 4 (depends on 1)

The method of claim 1, wherein RA and RB are the same.

### Claim 5 (depends on 4)

The method of claim 4, wherein RA and RB are isopropyl or tolyl.

### Claim 6 (depends on 1)

The method of claim 1, wherein the one or more compounds of formula VII are one or more of ethanethiol or n-propanethiol.

### Claim 7

A method for preparing a vinylidene terminated polyolefin, comprising:
(a) ionizing a polyolefin in the presence of a Lewis acid or mixture of Lewis acids to form an ionized polyolefin;
(b) reacting the ionized polyolefin from step (a) with one or more disulfides to form an intermediate; and
(c) reacting the intermediate of step (b) with one or more alcohols or amines.

### Claim 8 (depends on 7)

The method of claim 7, wherein the vinylidene terminated polyolefin is a vinylidene terminated polyisobutylene.

### Claim 9 (depends on 7)

The method of claim 7, wherein the intermediate of step (b) is reacted with one or more alcohols.

### Claim 10 (depends on 9)

The method of claim 9, wherein the one or more alcohols are of the formula:
R—OH
wherein R is alkyl of 1-8 carbons.

### Claim 11 (depends on 10)

The method of claim 10, wherein the one or more alcohols are one or more of methanol, ethanol, isopropanol, 2-ethylhexanol, or sec-butanol.

### Claim 12 (depends on 7)

The method of claim 7, wherein the one or more disulfides are a compound of formula I:
RA—S—S—RB I
wherein RA and RB are each, independently, alkyl, aryl, aralkyl, alkaryl,
wherein:
m is 1-3; n is 1-3; p is 1-3;
X is halo or a pseudohalide;
Rx is alkyl or aryl;
R3 is tert-butyl; and
R4 and R5 are each, independently, alkyl, aryl, aralkyl, or alkaryl.

### Claim 13 (depends on 12)

The method of claim 12, wherein RA and RB are methyl, ethyl, tert-butyl, isopropyl, or tolyl.

### Claim 14 (depends on 13)

The method of claim 13, wherein RA and RB are isopropyl.

### Claim 15 (depends on 1)

The method of claim 1, wherein the ionized polyolefin is formed by adding a Lewis acid to a tert-halide terminated polyolefin or adding a Lewis acid and a proton source to a preformed polyolefin.

### Claim 16 (depends on 7)

The method of claim 7, wherein the ionized polyolefin is formed by adding a Lewis acid to a tert-halide terminated polyolefin or adding a Lewis acid and a proton source to a preformed polyolefin.

### Claim 17 (depends on 1)

The method of claim 1, wherein the ionized polyolefin is a quasiliving carbocationic polyolefin and the method is performed under quasiliving carbocationic polymerization conditions.

### Claim 18 (depends on 17)

The method of claim 17, wherein the quasiliving carbocationic polyolefin is prepared by adding a Lewis acid and a monomer to an initiator in the presence of an electron donor, common ion salt, or common ion salt precursor.

### Claim 19 (depends on 18)

The method of claim 18, wherein the initiator is 2-chloro-2,4,4-trimethylpentane, 1,3-di(2-chloro-2-propyl)-5-tert-butylbenzene, or dicumyl chloride.

### Claim 20 (depends on 18)

The method of claim 18, wherein the monomer is isobutylene or styrene.

### Claim 21 (depends on 18)

The method of claim 18, wherein the electron donor is pyridine or a pyridine derivative.

### Claim 22 (depends on 21)

The method of claim 21, wherein the electron donor is 2,6-dimethylpyridine, 2,4-dimethylpyridine, or 2,6-di-tert-butylpyridine.

### Claim 23 (depends on 18)

The method of claim 18, wherein the common ion salt precursor is tetrabutylammonium chloride or tetrabutylammonium iodide.

### Claim 24 (depends on 7)

The method of claim 7, wherein the ionized polyolefin is a quasiliving carbocationic polyolefin and the method is performed under quasiliving carbocationic polymerization conditions.

### Claim 25 (depends on 24)

The method of claim 24, wherein the quasiliving carbocationic polyolefin is prepared by adding a Lewis acid and a monomer to an initiator in the presence of an electron donor, common ion salt, or common ion salt precursor.

### Claim 26 (depends on 25)

The method of claim 25, wherein the initiator is 2-chloro-2,4,4-trimethylpentane, 1,3-di(2-chloro-2-propyl)-5-tert-butylbenzene, or dicumyl chloride.

### Claim 27 (depends on 25)

The method of claim 25, wherein the monomer is isobutylene or styrene.

### Claim 28 (depends on 25)

The method of claim 25, wherein the electron donor is pyridine or a pyridine derivative.

### Claim 29 (depends on 25)

The method of claim 25, wherein the electron donor is 2,6-dimethylpyridine, 2,4-dimethylpyridine, or 2,6-di-tert-butylpyridine.

### Claim 30 (depends on 25)

The method of claim 25, wherein the common ion salt precursor is tetrabutylammonium chloride or tetrabutylammonium iodide.

### Claim 31 (depends on 1)

The method of claim 1, wherein the Lewis acid is a titanium tetrahalide, a boron trihalide, an aluminum trihalide, a tin tetrahalide, zinc chloride, or ethyl aluminum dichloride, or a mixture thereof.

### Claim 32 (depends on 31)

The method of claim 31, wherein the Lewis acid is titanium tetrachloride.

### Claim 33 (depends on 1)

The method of claim 1, wherein a mixture of Lewis acids is used.

### Claim 34 (depends on 33)

The method of claim 33, wherein the mixture of Lewis acids is a mixture of an aluminum (III) halide and a trialkyl aluminum compound.

### Claim 35 (depends on 7)

The method of claim 7, wherein the Lewis acid is a titanium tetrahalide, a boron trihalide, an aluminum trihalide, a tin tetrahalide, zinc chloride, or ethyl aluminum dichloride, or a mixture thereof.

### Claim 36 (depends on 35)

The method of claim 35, wherein the Lewis acid is titanium tetrachloride.

### Claim 37 (depends on 7)

The method of claim 7, wherein a mixture of Lewis acids is used.

### Claim 38 (depends on 37)

The method of claim 37, wherein the mixture of Lewis acids is a mixture of aluminum (III) bromide and trimethyl aluminum.

### Claim 39 (depends on 1)

The method of claim 1, wherein a diluent is used.

### Claim 40 (depends on 39)

The method of claim 39, wherein the diluent is an alkane, an alkyl halide, or a mixture thereof.

### Claim 41 (depends on 7)

The method of claim 7, wherein a diluent is used.

### Claim 42 (depends on 41)

The method of claim 41, wherein the diluent is an alkane, an alkyl halide, or a mixture thereof.

### Claim 43 (depends on 1)

The method of claim 1, wherein the method is performed at a temperature from about −120° C. to about 0° C.

### Claim 44 (depends on 43)

The method of claim 43, wherein the temperature is from about −70° C. to about −40° C.

### Claim 45 (depends on 7)

The method of claim 7, wherein the method is performed at a temperature from about −120° C. to about 0° C.

### Claim 46 (depends on 45)

The method of claim 45, wherein the temperature is from about −70° C. to about −40° C.

### Claim 47 (depends on 1)

The method of claim 1, wherein the Lewis acid or mixture of Lewis acids are present at a molar concentration of from about 0.5 to about 20 times chain-end molar concentration.

### Claim 48 (depends on 7)

The method of claim 7, wherein the Lewis acid or mixture of Lewis acids are present at a molar concentration of from about 0.5 to about 20 times chain-end molar concentration.

### Claim 49 (depends on 18)

The method of claim 18, wherein step (b) is added after high conversion of the monomer.

### Claim 50 (depends on 25)

The method of claim 25, wherein step (b) is added after high conversion of the monomer.

### Claim 51 (depends on 1)

The method of claim 1, wherein the compound of formula V formed is at least 70 mole percent of all products.

### Claim 52 (depends on 7)

The method of claim 7, wherein the vinylidene terminated polyolefin formed is at least 70 mole percent of all products.